Proceedings of nanoGe September Meeting 2015 (NFM15)
Publication date: 8th June 2015
Chalcogenide-based semiconductors demonstrate a great potential for the development of cost-efficient photovoltaic technologies. Chalcopyrite-based technologies (CIGS: Cu(In,Ga)(S,Se)2) are already at industrial stage, and the emerging kesterite-based technologies (CZTS: Cu2ZnSn(S,Se)4) are under development. For the former, record cells (21.7% (ZSW, 2014)) have reached efficiencies comparable to leading PV Si technologies , and large area commercially available modules have efficiencies in the 13-14% range. For the latter, kesterites constitute a potential alternative more suited for the future mass deployment of these technologies, these semiconductors being constituted only from abundant elements in the earth’s crust. In this case, the lower level of maturity of these technologies is reflected in the lower efficiencies achieved, with a record cell efficiency at 12.7% (IBM, 2014), and up-scaling of kesterite based processes is still a challenge. This work reviews the advanced characterization performed on electrodeposition (ED) based chalcogenide processes manufactured at the company NEXCIS. ED is a process very well suited for industrial implementation at mass production stages, and has a significant potential for cost reduction. Developed processes involve ED of multilayer metallic stacks followed by a rapid thermal process (RTP) under elemental Se and/or S atmospheres. This allows avoiding toxic and more expensive H2Se and H2S compounds that are typically used in the industrial production of CIGS based modules (which are mainly based in high vacuum processes with high CAPEX costs). In the case of CIGS, the precise control of the S and Ga content profiles in the absorbers is a critical feature to achieve high efficiency devices. With this objective, Raman scattering based methodologies in combination with Photoluminescence (PL) measurements have been developed for the quantitative assessment of the chemical composition of the absorbers and detection of local inhomogeneities. Optimisation of the manufacturing processes at NEXCISlead to a record cell efficiency of 17.3% (0.5cm² area), which constitutes the highest efficiency value reported for solution based CIGS devices. Scalability of the processes has also been demonstrated, with the production of 60x120 cm2 modules with 14.0% aperture area efficacy. The extension of these processes for the development of kesterite-based devices will also be reviewed: in this case adaptation of chemical processes developed for the specific removal of secondary phases has allowed achieving cell efficiencies up to 8.5%, which constitute a world record for ED-based kesterite devices. These data confirm the strong potential of ED based processes for the development of advanced cost-efficient PV technologies.
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